Skip to main content
SpringerLink
Log in

OH-initiated oxidation mechanism and kinetics of organic sunscreen benzophenone-3: A theoretical study

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

Benzophenone-3 (BP-3), as an important organic UV filter, is widely used in the sunscreen, cosmetic, and personal care products. The chemical reaction mechanism and kinetics of BP-3 degradation initiated by hydroxyl (OH) radical was investigated in the atmosphere based on the density functional theory (DFT). The results showed that the OH radical is more easily added to the C3 position of the aromatic ring (pathway 3), while the H atom abstraction from the OH group on the aromatic ring (pathway 23) is an energetically favorable reaction pathway. At ambient temperature, 298 K, the overall rate constant for the primary reaction is about 1.50 × 10−10 cm3 mol−1 s−1 with the lifetime of 1.92 h. OH addition reactions play the key role in the OH-initiated reaction of BP-3. The study is helpful for better understanding of the removal, transformation, and fate of BP-3 in the atmosphere.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Azofra, L. M., Alkorta, I., Elguero, J., & Toro-Labbe, A. (2012). Mechanisms of formation of hemiacetals: Intrinsic reactivity analysis. The Journal of Physical Chemistry A, 116, 8250–8259. DOI: 10.1021/jp304495f.

    Article  CAS  Google Scholar 

  • Bai, J., Sun, X., Zhang, C., Gong, C., Hu, J., & Zhang, J. (2014). Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere. Journal of Environmental Sciences, 26, 181–188. DOI: 10.1016/s1001–0742(13)60396–4.

    Article  CAS  Google Scholar 

  • Brausch, J. M., & Rand, G. M. (2011). A review of personal care products in the aquatic environment: Environmental concentrations and toxicity. Chemosphere, 82, 1518–1532. DOI: 10.1016/j.chemosphere.2010.11.018.

    Article  CAS  Google Scholar 

  • Burnett, M. E., & Wang, S. Q. (2011). Current sunscreen controversies: a critical review. Photodermatology, Photoimmunology & Photomedicine, 27, 58–67. DOI: 10.1111/j.1600- 0781.2011.00557.x.

    Article  CAS  Google Scholar 

  • Caliman, F. A., & Gavrilescu, M. (2009). Pharmaceuticals, personal care products and endocrine disrupting agents in the environment — a review. CLEAN — Soil, Air, Water, 37, 277–303. DOI: 10.1002/clen.200900038.

    Article  CAS  Google Scholar 

  • Canneaux, S., Bohr, F., & Henon, E. (2014). KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results. Journal of Computational Chemistry, 35, 82–93. DOI: 10.1002/jcc.23470.

    Article  CAS  Google Scholar 

  • Cao, H., He, M., Han, D., Sun, Y., Zhao, S., Ma, H., & Yao, S. (2012). Mechanistic and kinetic study on the reaction of 2;4-dibrominated diphenyl ether (BDE-7) with OH radicals. Computational and Theoretical Chemistry, 983, 31–37. DOI: 10.1016/j.comptc.2011.12.017.

    Article  CAS  Google Scholar 

  • Cao, H., He, M., Han, D., Li, J., Li, M., Wang, W., & Yao, S. (2013). OH-initiated oxidation mechanisms and kinetics of 2,4,4/-tribrominated diphenyl ether. Environmental Science & Technology, 47, 8238–8247. DOI: 10.1021/es400088v.

    CAS  Google Scholar 

  • Chan, B., & Radom, L. (2012). Approaches for obtaining accurate rate constants for hydrogen abstraction by a chlorine atom. The Journal of Physical Chemistry A, 116, 3745–3752. DOI: 10.1021/jp3007409.

    Article  CAS  Google Scholar 

  • Dang, J., Shi, X., Zhang, Q., Hu, J., & Wang, W. (2015). Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene. Science of the Total Environment, 505, 787–794. DOI: 10.1016/j.scitotenv.2014.10.081.

    Article  CAS  Google Scholar 

  • Duirk, S. E., Bridenstine, D. R., & Leslie, D. C. (2013). Reaction of benzophenone UV filters in the presence of aqueous chlorine: Kinetics and chloroform formation. Water Research, 47, 579–587. DOI: 10.1016/j.watres.2012.10.021.

    Article  CAS  Google Scholar 

  • Fent, K., Zenker, A., & Rapp, M. (2010). Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland. Environmental Pollution, 158, 1817–1824. DOI: 10.1016/j.envpol.2009.11.005.

    Article  CAS  Google Scholar 

  • Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, O. Foresman, J. B., Ortiz, J. V., Cioslowski, J., & Fox, D. J. (2009). Gaussian 09, Revision A.1 [computer software]. Wallingford, CT, USA: Gaussian, Inc.

    Google Scholar 

  • Gago-Ferrero, P., Diaz-Cruz, M. S., & Barcelo, D. (2012). An overview of UV-absorbing compounds (organic UV filters) in aquatic biota. Analytical and Bioanalytical Chemistry, 404, 2597–2610. DOI: 10.1007/s00216–012–6067–7.

    Article  CAS  Google Scholar 

  • Gago-Ferrero, P., Demeestere, K., Diaz-Cruz, M. S., & Barcelo, D. (2013). Ozonation and peroxone oxidation of benzo- phenone-3 in water: Effect of operational parameters and identification of intermediate products. Science of the Total Environment, 443, 209–217. DOI: 10.1016/j.scitotenv.2012. 10.006.

    Article  CAS  Google Scholar 

  • Kaiser, D., Sieratowicz, A., Zielke, H., Oetken, M., Hollert, H., & Oehlmann, J. (2012a). Ecotoxicological effect characterisation of widely used organic UV filters. Environmental Pollution, 163, 84–90. DOI: 10.1016/j.envpol.2011.12.014.

    Article  CAS  Google Scholar 

  • Kaiser, D., Wappelhorst, O., Oetken, M., & Oehlmann, J. (2012b). Occurrence of widely used organic UV filters in lake and river sediments. Environmental Chemistry, 9, 139–147. DOI: 10.1071/en11076.

    Article  CAS  Google Scholar 

  • Kim, S., & Choi, K. (2014). Occurrences, toxicities, and ecological risks of benzophenone-3, a common component of organic sunscreen products: A mini-review. Environment International, 70, 143–157. DOI: 10.1016/j.envint.2014.05.015.

    Article  CAS  Google Scholar 

  • Li, C., Xie, H. B., Chen, J., Yang, X., Zhang, Y., & Qiao, X. (2014a). Predicting gaseous reaction rates of short chain chlorinated paraffins with OH: Overcoming the difficulty in experimental determination. Environmental Science & Technology, 48, 13808–13816. DOI: 10.1021/es504339r.

    Article  CAS  Google Scholar 

  • Li, P., Niu, W., Gao, T., & Wang, H. (2014b). Gas-phase water activation by Thatom: Reaction mechanisms and topological analysis. International Journal of Quantum Chemistry, 114, 760–768. DOI: 10.1002/qua.24651.

    Article  CAS  Google Scholar 

  • Liu, Y. S., Ying, G. G., Shareef, A., & Kookana, R. S. (2011). Photostability of the UV filter benzophenone-3 and its effect on the photodegradation of benzotriazole in water. Environmental Chemistry, 8, 581–588. DOI: 10.1071/en11068.

    Article  CAS  Google Scholar 

  • Liu, Y. S., Ying, G. G., Shareef, A., & Kookana, R. S. (2012). Biodegradation of the ultraviolet filter benzophenone-3 under different redox conditions. Environmental Toxicology and Chemistry, 31, 289–295. DOI: 10.1002/etc.749.

    Article  CAS  Google Scholar 

  • Lu, T., & Chen, F. (2012). Multiwfn: A multifunctional wave-function analyzer. Journal of Computational Chemistry, 33, 580–592. DOI: 10.1002/jcc.22885.

    Article  Google Scholar 

  • Manová, E., von Goetz, N., Hauri, U., Bogdal, C., & Hungerbühler, K. (2013). Organic UV filters in personal care products in Switzerland: A survey of occurrence and concentrations. International Journal of Hygiene and Environmental Health, 216, 508–514. DOI: 10.1016/j.ijheh.2012.08.003.

    Article  Google Scholar 

  • Rodil, R., Quintana, J. B., Concha-Grana, E., Lopez-Mahia, P., Muniategui-Lorenzo, S., & Prada-Rodriguez, D. (2012). Emerging pollutants in sewage, surface and drinking water in Galicia (NW Spain). Chemosphere, 86, 1040–1049. DOI: 10.1016/j.chemosphere.2011.11.053.

    Article  CAS  Google Scholar 

  • Tsui, M. M. P., Leung, H. W., Lam, P. K. S., & Murphy, M. B. (2014a). Seasonal occurrence, removal efficiencies and preliminary risk assessment of multiple classes of organic UV filters in wastewater treatment plants. Water Research, 53, 58–67. DOI: 10.1016/j.watres.2014.01.014.

    Article  CAS  Google Scholar 

  • Tsui, M. M. P., Leung, H. W., Wai, T. C., Yamashita, N., Taniyasu, S., Liu, W., Lam, P. K. S., & Murphy, M. B. (2014b). Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries. Water Research, 67, 55–65. DOI: 10.1016/j.watres.2014.09.013.

    Article  CAS  Google Scholar 

  • US EPA (2012). Estimation programs interface suite for Microsoft Windows, Version 4.11 [computer software]. Washington, DC, USA: United States Environmental Protection Agency.

    Google Scholar 

  • Wang, L., & Kannan, K. (2013). Characteristic profiles of benzonphenone-3 and its derivatives in urine of children and adults from the United States and China. Environmental Science & Technology, 47, 12532–12538. DOI: 10.1021/es4032908.

    Article  CAS  Google Scholar 

  • Wang, S., Hao, C., Gao, Z., Chen, J., & Qiu, J. (2014). Theoretical investigations on direct photolysis mechanisms of polychlorinated diphenyl ethers. Chemosphere, 111, 7–12. DOI: 10.1016/j.chemosphere.2014.03.040.

    Article  CAS  Google Scholar 

  • Wei, X., Chen, J., Xie, Q., Zhang, S., Ge, L., & Qiao, X. (2013). Distinct photolytic mechanisms and products for different dissociation species of ciprofloxacin. Environmental Science & Technology, 47, 4284–4290. DOI: 10.1021/es400425b.

    Article  CAS  Google Scholar 

  • Wu, P. Z., Li, J., Li, S. J., & Tao, F. M. (2012). Theoretical study of mechanism and kinetics for the addition of hydroxyl radical to phenol. Science China-Chemistry, 55, 270–276. DOI: 10.1007/s11426–011–4380–1.

    Article  CAS  Google Scholar 

  • Xie, H. B., Li, C., He, N., Wang, C., Zhang, S., & Chen, J. (2014). Atmospheric chemical reactions of monoethanolamine initiated by OH radical: Mechanistic and kinetic study. Environmental Science & Technology, 48, 1700–1706. DOI: 10.1021/es405110t.

    Article  CAS  Google Scholar 

  • Yang, B., & Ying, G. G. (2013). Oxidation of benzophenone- 3 during water treatment with ferrate(VI). Water Research, 47, 2458–2466. DOI: 10.1016/j.watres.2013.02.018.

    Article  CAS  Google Scholar 

  • Zhang, C., Yang, W., Bai, J., Zhao, Y., Gong, C., Sun, X., Zhang, Q., & Wang, W. (2012a). Mechanism and kinetic study on the gas-phase reactions of OH radical with carbamate insecticide isoprocarb. Atmospheric Environment, 60, 460–466. DOI: 10.1016/j.atmosenv.2012.07.015.

    Article  CAS  Google Scholar 

  • Zhang, C., Zhao, Y., Bai, J., Gong, C., & Sun, X. (2012b). Mechanism and kinetic study on the OH-initiated degradation of 2,3,7,8-tetrachlorinated dibenzofuran in atmosphere. Science of the Total Environment, 435–436, 53–60. DOI: 10.1016/j.scitotenv.2012.07.007.

    Article  Google Scholar 

  • Zhang, H., Xie, H., Chen, J., & Zhang, S. (2015). Prediction of hydrolysis pathways and kinetics for antibiotics under environmental pH conditions: A Quantum chemical study on cephradine. Environmental Science & Technology, 49, 1552–1558. DOI: 10.1021/es505383b.

    Article  CAS  Google Scholar 

  • Zhou, J., Chen, J., Liang, C. H., Xie, Q., Wang, Y. N., Zhang, S., Qiao, X., & Li, X. (2011). Quantum chemical investigation on the mechanism and kinetics of PBDE photooxidation by OH: A case study for BDE-15. Environmental Science & Technology, 45, 4839–4845. DOI: 10.1021/es200087w.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Environmental and Safety Engineering, Changzhou University, Changzhou, 213164, China

    Ming-Guo Peng, Hua-Jie Li, Er-Deng Du, Dong-Dong Li & Jing Zhou

  2. Information Center, Changzhou University, Changzhou, 213164, China

    Hong-Qi Feng & Juan-Lin Wang

Authors
  1. Ming-Guo Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hua-Jie Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Er-Deng Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hong-Qi Feng
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Juan-Lin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dong-Dong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jing Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Er-Deng Du.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Peng, MG., Li, HJ., Du, ED. et al. OH-initiated oxidation mechanism and kinetics of organic sunscreen benzophenone-3: A theoretical study. Chem. Pap. 70, 856–868 (2016). https://doi.org/10.1515/chempap-2016-0003

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1515/chempap-2016-0003

Keywords

Search

Navigation